EP2768893A2 - Azeotrope-like compositions of e-1-chloro-2,3,3,3-tetrafluoropropene and uses thereof - Google Patents

Azeotrope-like compositions of e-1-chloro-2,3,3,3-tetrafluoropropene and uses thereof

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Publication number
EP2768893A2
EP2768893A2 EP12784174.0A EP12784174A EP2768893A2 EP 2768893 A2 EP2768893 A2 EP 2768893A2 EP 12784174 A EP12784174 A EP 12784174A EP 2768893 A2 EP2768893 A2 EP 2768893A2
Authority
EP
European Patent Office
Prior art keywords
azeotrope
hfo
compositions
composition
hcfo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12784174.0A
Other languages
German (de)
French (fr)
Other versions
EP2768893B1 (en
Inventor
Mark L. Robin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemours Co FC LLC
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2768893A2 publication Critical patent/EP2768893A2/en
Application granted granted Critical
Publication of EP2768893B1 publication Critical patent/EP2768893B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0057—Polyhaloalkanes
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0092—Gaseous extinguishing substances, e.g. liquefied gases, carbon dioxide snow
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/504—Azeotropic mixtures containing halogenated solvents all solvents being halogenated hydrocarbons
    • C11D7/5054—Mixtures of (hydro)chlorofluorocarbons and (hydro) fluorocarbons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/56—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/32—The mixture being azeotropic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/918—Halocarbon

Definitions

  • the present disclosure relates to azeotrope-like compositions of E- 1 -chloro-2,3,3,3-tetrafluoropropene.
  • CFCs chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • thermoplastic and thermoset foams heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
  • HFCs hydrofluorocarbons
  • the HFCs do not contribute to the destruction of stratospheric ozone, but are of concern due to their contribution to the "greenhouse effect", i.e., they contribute to global warming. As a result of their contribution to global warming, the HFCs have come under scrutiny, and their widespread use may also be limited in the future. Thus, there is a need for compositions that do not contribute to the destruction of stratospheric ozone and also have low global warming potentials (GWPs).
  • GWPs global warming potentials
  • This application includes two different types of azeotrope-like mixtures.
  • composition consisting essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
  • FIG. 1 - FIG. 1 is a graphical representation of azeotrope-like
  • FIG. 2 - FIG. 2 is a graphical representation of azeotrope-like
  • a pure single component or an azeotropic or azeotrope-like mixture is desirable.
  • a blowing agent composition also known as foam expansion agents or foam expansion compositions
  • the composition may change during its application in the foam forming process. Such change in composition could detrimentally affect processing or cause poor performance in the application.
  • a refrigerant is often lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the refrigerant may be released to the atmosphere during maintenance procedures on refrigeration equipment.
  • the refrigerant is not a pure single component or an azeotropic or azeotrope-like composition
  • the refrigerant composition may change when leaked or discharged to the atmosphere from the refrigeration equipment.
  • HFO-1336mzz may exist as one of two configurational isomers, E or Z.
  • HFO-1336mzz as used herein refers to the isomers, Z-HFO- 1336mzz or E-HFO-1336mzz, as well as any combinations or mixtures of such isomers.
  • HFO-1438mzz may exist as one of two configurational isomers, E or Z.
  • HFO-1438mzz as used herein refers to the isomers, Z-HFO- 1438mzz or E-HFO-1438mzz, as well as any combinations or mixtures of such isomers.
  • HCFO-1224yd may exist as one of two configurational isomers, E or Z.
  • HCFO-1224yd as used herein refers to the isomers, Z-HCFO-1224yd or E-HCFO-1224yd, as well as any combinations or mixtures of such isomers.
  • E-HFO-1336mzz is a known compound, and can be made through the reaction of 1 ,2-dichloro-1 ,1 ,4,4,4-pentafluorobutane with dried KF in distilled tetramethylene sulphone, such as disclosed in U.S. Patent No. 5,463,150.
  • E-HCFO-1224yd is a known compound, and can be made by dehydrofluorinating CH 2 CICF 2 CF 3 (HCFC-235cb) in the presence of a dehydrofluorination catalyst, such as disclosed in U.S. Patent Publication No. 2010-0076231 .
  • This application includes azeotrope-like compositions comprising E- HCFO-1224yd.
  • the composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
  • the composition consists essentially of (a) E-HCFO-1224yd and (b) E-HFO-1336mzz; wherein the E-HFO-1336mzz is present in an effective amount to form an azeotrope- like mixture with E-HCFO-1224yd.
  • the composition consists essentially of (a) E-HCFO-1224yd and (b) E-HFO-1438mzz; wherein the E-HFO-1438mzz is present in an effective amount to form an azeotrope- like mixture with E-HCFO-1224yd.
  • effective amount an amount of E-HFO-1336mzz or E- HFO-1438mzz, which, when combined with E-HCFO-1224yd, results in the formation of an azeotrope-like mixture.
  • This definition includes the amounts of each component, which amounts may vary depending on the pressure applied to the composition so long as the azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points. Therefore, effective amount includes the amounts, such as may be expressed in weight or mole percentages, of each component of the compositions of the instant invention which form azeotrope-like compositions at temperatures or pressures other than as described herein.
  • an azeotropic composition is an admixture of two or more different components which, when in liquid form under a given pressure, will boil at a substantially constant temperature, which temperature may be higher or lower than the boiling temperatures of the individual components, and which will provide a vapor composition essentially identical to the overall liquid composition undergoing boiling, (see, e.g., M. F. Doherty and M.F. Malone, Conceptual Design of
  • an azeotropic composition is that at a given pressure, the boiling point of the liquid composition is fixed and that the composition of the vapor above the boiling composition is essentially that of the overall boiling liquid composition (i.e., no
  • an azeotropic composition may be defined in terms of the unique relationship that exists among the components or in terms of the compositional ranges of the components or in terms of exact weight percentages of each component of the composition characterized by a fixed boiling point at a specified pressure.
  • an azeotrope-like composition means a composition that behaves like an azeotropic composition (i.e., has constant boiling characteristics or a tendency not to fractionate upon boiling or evaporation). Hence, during boiling or evaporation, the vapor and liquid compositions, if they change at all, change only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which during boiling or evaporation, the vapor and liquid compositions change to a substantial degree.
  • compositions with a difference in dew point pressure and bubble point pressure of less than or equal to 5 percent (based upon the bubble point pressure) is considered to be azeotrope-like.
  • Relative volatility is the ratio of the volatility of component 1 to the volatility of component 2.
  • the ratio of the mole fraction of a component in vapor to that in liquid is the volatility of the component.
  • VLE vapor-liquid equilibrium
  • the isothermal method requires measurement of the total pressure of mixtures of known composition at constant temperature. In this procedure, the total absolute pressure in a cell of known volume is measured at a constant temperature for various compositions of the two compounds.
  • the isobaric method requires measurement of the
  • NRTL Non-Random, Two-Liquid
  • the NRTL equation can sufficiently predict the relative volatilities of the E-HCFO-1224yd/E-HFO-1336mzz compositions and the E-HCFO-1224yd/E-HFO-1438mzz compositions of the present invention and can therefore predict the behavior of these mixtures in multi-stage separation equipment such as distillation columns.
  • FIG. 1 The pressures measured versus the compositions in the PTx cell for E-HFO-1336mzz/E-HCFO-1224yd mixture are shown in FIG. 1 , which graphically illustrates the formation of azeotrope-like compositions of E- HFO-1336mzz and E-HCFO-1224yd at 31 .7 °C, as indicated by mixtures of about 1 to 99 mole % E-HFO-1336mzz and about 99 to 1 mole % E- HCFO-1224yd at pressures ranging from about 28 psia to about 36 psia.
  • azeotrope-like compositions consisting essentially of 1 -99 mole % E-HFO-1336mzz and 99-1 mole % E-HCFO- 1224yd are formed at temperatures ranging from about -40 °C to about 120 °C (i.e., over this temperature range, the difference in dew point pressure and bubble point pressure of the composition at a particular temperature is less than or equal to 5 percent (based upon the bubble point pressure)).
  • azeotrope-like compositions are listed in Table 1 . Some more embodiments of azeotrope-like compositions are listed in Table 2.
  • FIG. 2 The pressures measured versus the compositions in the PTx cell for E-HFO-1438mzz/E-HCFO-1224yd mixture are shown in FIG. 2, which graphically illustrates the formation of azeotrope-like compositions of E- HFO-1438mzz and E-HCFO-1224yd at 31 .8 °C, as indicated by mixtures of about 1 to 33 mole % E-HFO-1438mzz and about 99 to 67 mole % E- HCFO-1224yd at pressures ranging from about 25 psia to about 28 psia, and mixtures of about 84 to 99 mole % E-HFO-1438mzz and about 16 to 1 mole % E-HCFO-1224yd at pressures ranging from about 16 psia to about 19 psia.
  • azeotrope-like compositions consisting essentially of 1 -99 mole % E-HFO-1438mzz and 99-1 mole % E-HCFO- 1224yd are formed at temperatures ranging from about -40 °C to about 140 °C (i.e., over this temperature range, the difference in dew point pressure and bubble point pressure of the composition at a particular temperature is less than or equal to 5 percent (based upon the bubble point pressure)).
  • azeotrope-like compositions are listed in Table 3. Some more embodiments of azeotrope-like compositions are listed in Table 4.
  • azeotrope-like compositions of the present invention can be prepared by any convenient method including mixing or combining the desired amounts.
  • an azeotrope-like composition can be prepared by weighing the desired component amounts and thereafter combining them in an appropriate container.
  • azeotrope-like compositions of the present invention can be used in a wide range of applications, including their use as aerosol propellants, refrigerants, solvents, cleaning agents, blowing agents (foam expansion agents) for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
  • One embodiment of this invention provides a process for preparing a thermoplastic or thermoset foam.
  • the process comprises using an azeotrope-like composition as a blowing agent, wherein said azeotrope- like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E- HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
  • Another embodiment of this invention provides a process for producing refrigeration.
  • the process comprises condensing an azeotrope- like composition and thereafter evaporating said azeotrope-like
  • azeotrope-like composition in the vicinity of the body to be cooled, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
  • Another embodiment of this invention provides a process using an azeotrope-like composition as a solvent, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E- HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
  • Another embodiment of this invention provides a process for producing an aerosol product.
  • the process comprises using an azeotrope- like composition as a propellant, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz;
  • said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
  • Another embodiment of this invention provides a process using an azeotrope-like composition as a heat transfer media, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
  • Another embodiment of this invention provides a process for extinguishing or suppressing a fire.
  • the process comprises using an azeotrope-like composition as a fire extinguishing or suppression agent, wherein said azeotrope-like composition consists essentially of (a) E- HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
  • Another embodiment of this invention provides a process using an azeotrope-like composition as dielectrics, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E- HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.

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Abstract

Azeotrope-like compositions are disclosed. The azeotrope-like compositions are mixtures of E-1-chloro-2,3,3,3-tetrafluoropropene with E-1,1,1,4,4,4-hexafluoro-2-butene or E-1,1,1,4,4,5,5,5-octafluoro-2-pentene. Also disclosed is a process of preparing a thermoplastic or thermoset foam by using such azeotrope-like compositions as blowing agents. Also disclosed is a process of producing refrigeration by using such azeotrope-like compositions. Also disclosed is a process of using such azeotrope-like compositions as solvents. Also disclosed is a process of producing an aerosol product by using such azeotrope-like compositions. Also disclosed is a process of using such azeotrope-like compositions as heat transfer media. Also disclosed is a process of extinguishing or suppressing a fire by using such azeotrope-like compositions. Also disclosed is a process of using such azeotrope-like compositions as dielectrics.

Description

TITLE OF INVENTION
AZEOTROPE-LIKE COMPOSITIONS OF E-1 -CHLORO-2,3,3,3-TETRAFLUOROPROPENE AND USES THEREOF
This application claims priority of U.S. Patent Applications
61/549265 and 61/549267 filed October 20, 201 1 .
BACKGROUND OF THE INVENTION
Field of the Disclosure
The present disclosure relates to azeotrope-like compositions of E- 1 -chloro-2,3,3,3-tetrafluoropropene.
Description of Related Art
Many industries have been working for the past few decades to find replacements for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The CFCs and HCFCs have been employed in a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for
thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. In the search for replacements for these versatile compounds, many industries have turned to the use of hydrofluorocarbons (HFCs).
The HFCs do not contribute to the destruction of stratospheric ozone, but are of concern due to their contribution to the "greenhouse effect", i.e., they contribute to global warming. As a result of their contribution to global warming, the HFCs have come under scrutiny, and their widespread use may also be limited in the future. Thus, there is a need for compositions that do not contribute to the destruction of stratospheric ozone and also have low global warming potentials (GWPs). Certain hydrofluoroolefins, such as 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (CF3CH=CHCF3, FC-1336mzz, HFO-1336mzz) and 1 ,1 ,1 ,4,4,5,5,5- octafluoro-2-pentene (CF3CH=CHCF2CF3, HFO-1438mzz), are believed to meet both goals. SUMMARY OF THE INVENTION
This application includes two different types of azeotrope-like mixtures.
This disclosure provides a composition consisting essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
BRIEF SUMMARY OF THE DRAWINGS
FIG. 1 - FIG. 1 is a graphical representation of azeotrope-like
compositions of E-HFO-1336mzz and E-HCFO-1224yd at a temperature of about 31 .7 °C. FIG. 2 - FIG. 2 is a graphical representation of azeotrope-like
compositions of E-HFO-1438mzz and E-HCFO-1224yd at a temperature of about 31 .8 °C.
DETAILED DESCRIPTION OF THE INVENTION
In many applications, the use of a pure single component or an azeotropic or azeotrope-like mixture is desirable. For example, when a blowing agent composition (also known as foam expansion agents or foam expansion compositions) is not a pure single component or an azeotropic or azeotrope-like mixture, the composition may change during its application in the foam forming process. Such change in composition could detrimentally affect processing or cause poor performance in the application. Also, in refrigeration applications, a refrigerant is often lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the refrigerant may be released to the atmosphere during maintenance procedures on refrigeration equipment. If the refrigerant is not a pure single component or an azeotropic or azeotrope-like composition, the refrigerant composition may change when leaked or discharged to the atmosphere from the refrigeration equipment. The change in refrigerant composition may cause the refrigerant to become flammable or to have poor refrigeration performance. Accordingly, there is a need for using azeotropic or azeotrope-like mixtures in these and other applications, for example azeotropic or azeotrope-like mixtures containing E-1 -chloro-2,3,3,3-tetrafluoropropene (E-CF3CF=CHCI, E-
HCFO-1224yd) and E-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (E-CF3CH=CHCF3, E-FC-1336mzz, E-HFO-1336mzz), or E-HCFO-1224yd and E- 1 ,1 ,1 ,4,4,5,5,5-octafluoro-2-pentene (E-CF3CH=CHCF2CF3> E-HFO- 1438mzz).
Before addressing details of embodiments described below, some terms are defined or clarified.
HFO-1336mzz may exist as one of two configurational isomers, E or Z. HFO-1336mzz as used herein refers to the isomers, Z-HFO- 1336mzz or E-HFO-1336mzz, as well as any combinations or mixtures of such isomers.
HFO-1438mzz may exist as one of two configurational isomers, E or Z. HFO-1438mzz as used herein refers to the isomers, Z-HFO- 1438mzz or E-HFO-1438mzz, as well as any combinations or mixtures of such isomers.
1 -chloro-2,3,3,3-tetrafluoropropene (CF3CF=CHCI, HCFO-1224yd) may exist as one of two configurational isomers, E or Z. HCFO-1224yd as used herein refers to the isomers, Z-HCFO-1224yd or E-HCFO-1224yd, as well as any combinations or mixtures of such isomers.
As used herein, the terms "comprises," "comprising," "includes,"
"including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
Also, use of "a" or "an" are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
E-HFO-1336mzz is a known compound, and can be made through the reaction of 1 ,2-dichloro-1 ,1 ,4,4,4-pentafluorobutane with dried KF in distilled tetramethylene sulphone, such as disclosed in U.S. Patent No. 5,463,150. E-HFO-1438mzz is a known compound, and can be made through the reaction between CF3CH=CHF and CF2=CF2 in the presence of a Lewis acid catalyst (e.g., SbF5), such as disclosed in PCT Patent
Application Publication WO 2008/057513 A1 .
E-HCFO-1224yd is a known compound, and can be made by dehydrofluorinating CH2CICF2CF3 (HCFC-235cb) in the presence of a dehydrofluorination catalyst, such as disclosed in U.S. Patent Publication No. 2010-0076231 .
This application includes azeotrope-like compositions comprising E- HCFO-1224yd.
In some embodiments of this invention, the composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
In some embodiments of this invention, the composition consists essentially of (a) E-HCFO-1224yd and (b) E-HFO-1336mzz; wherein the E-HFO-1336mzz is present in an effective amount to form an azeotrope- like mixture with E-HCFO-1224yd.
In some embodiments of this invention, the composition consists essentially of (a) E-HCFO-1224yd and (b) E-HFO-1438mzz; wherein the E-HFO-1438mzz is present in an effective amount to form an azeotrope- like mixture with E-HCFO-1224yd.
By effective amount is meant an amount of E-HFO-1336mzz or E- HFO-1438mzz, which, when combined with E-HCFO-1224yd, results in the formation of an azeotrope-like mixture. This definition includes the amounts of each component, which amounts may vary depending on the pressure applied to the composition so long as the azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points. Therefore, effective amount includes the amounts, such as may be expressed in weight or mole percentages, of each component of the compositions of the instant invention which form azeotrope-like compositions at temperatures or pressures other than as described herein. As recognized in the art, an azeotropic composition is an admixture of two or more different components which, when in liquid form under a given pressure, will boil at a substantially constant temperature, which temperature may be higher or lower than the boiling temperatures of the individual components, and which will provide a vapor composition essentially identical to the overall liquid composition undergoing boiling, (see, e.g., M. F. Doherty and M.F. Malone, Conceptual Design of
Distillation Systems, McGraw-Hill (New York), 2001 , 185-186, 351 -359).
Accordingly, the essential features of an azeotropic composition are that at a given pressure, the boiling point of the liquid composition is fixed and that the composition of the vapor above the boiling composition is essentially that of the overall boiling liquid composition (i.e., no
fractionation of the components of the liquid composition takes place). It is also recognized in the art that both the boiling point and the weight percentages of each component of the azeotropic composition may change when the azeotropic composition is subjected to boiling at different pressures. Thus, an azeotropic composition may be defined in terms of the unique relationship that exists among the components or in terms of the compositional ranges of the components or in terms of exact weight percentages of each component of the composition characterized by a fixed boiling point at a specified pressure.
For the purpose of this invention, an azeotrope-like composition means a composition that behaves like an azeotropic composition (i.e., has constant boiling characteristics or a tendency not to fractionate upon boiling or evaporation). Hence, during boiling or evaporation, the vapor and liquid compositions, if they change at all, change only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which during boiling or evaporation, the vapor and liquid compositions change to a substantial degree.
Additionally, azeotrope-like compositions exhibit dew point pressure and bubble point pressure with virtually no pressure differential. That is to say that the difference in the dew point pressure and bubble point pressure at a given temperature will be a small value. In this invention, compositions with a difference in dew point pressure and bubble point pressure of less than or equal to 5 percent (based upon the bubble point pressure) is considered to be azeotrope-like.
It is recognized in this field that when the relative volatility of a system approaches 1 .0, the system is defined as forming an azeotropic or azeotrope-like composition. Relative volatility is the ratio of the volatility of component 1 to the volatility of component 2. The ratio of the mole fraction of a component in vapor to that in liquid is the volatility of the component.
To determine the relative volatility of any two compounds, a method known as the PTx method can be used. The vapor-liquid equilibrium (VLE), and hence relative volatility, can be determined either isothermally or isobarically. The isothermal method requires measurement of the total pressure of mixtures of known composition at constant temperature. In this procedure, the total absolute pressure in a cell of known volume is measured at a constant temperature for various compositions of the two compounds. The isobaric method requires measurement of the
temperature of mixtures of known composition at constant pressure. In this procedure, the temperature in a cell of known volume is measured at a constant pressure for various compositions of the two compounds. Use of the PTx Method is described in detail in "Phase Equilibrium in Process Design", Wiley-lnterscience Publisher, 1970, written by Harold R. Null, on pages 124 to 126.
These measurements can be converted into equilibrium vapor and liquid compositions in the PTx cell by using an activity coefficient equation model, such as the Non-Random, Two-Liquid (NRTL) equation, to represent liquid phase nonidealities. Use of an activity coefficient equation, such as the NRTL equation is described in detail in "The Properties of Gases and Liquids," 4th edition, published by McGraw Hill, written by Reid, Prausnitz and Poling, on pages 241 to 387, and in "Phase Equilibria in Chemical Engineering," published by Butterworth Publishers, 1985, written by Stanley M. Walas, pages 165 to 244. Without wishing to be bound by any theory or explanation, it is believed that the NRTL equation, together with the PTx cell data, can sufficiently predict the relative volatilities of the E-HCFO-1224yd/E-HFO-1336mzz compositions and the E-HCFO-1224yd/E-HFO-1438mzz compositions of the present invention and can therefore predict the behavior of these mixtures in multi-stage separation equipment such as distillation columns.
It was found through experiments that E-HCFO-1224yd and E- HFO-1336mzz form azeotrope-like compositions.
To determine the relative volatility of this binary pair, the PTx method described above was used. The pressure in a PTx cell of known volume was measured at constant temperature for various binary compositions. These measurements were then reduced to equilibrium vapor and liquid compositions in the cell using the NRTL equation.
The pressures measured versus the compositions in the PTx cell for E-HFO-1336mzz/E-HCFO-1224yd mixture are shown in FIG. 1 , which graphically illustrates the formation of azeotrope-like compositions of E- HFO-1336mzz and E-HCFO-1224yd at 31 .7 °C, as indicated by mixtures of about 1 to 99 mole % E-HFO-1336mzz and about 99 to 1 mole % E- HCFO-1224yd at pressures ranging from about 28 psia to about 36 psia. According to calculation, azeotrope-like compositions consisting essentially of 1 -99 mole % E-HFO-1336mzz and 99-1 mole % E-HCFO- 1224yd are formed at temperatures ranging from about -40 °C to about 120 °C (i.e., over this temperature range, the difference in dew point pressure and bubble point pressure of the composition at a particular temperature is less than or equal to 5 percent (based upon the bubble point pressure)).
Some embodiments of azeotrope-like compositions are listed in Table 1 . Some more embodiments of azeotrope-like compositions are listed in Table 2.
Table 1 Azeotrope-like compositions
E-HFO-1336mzz/E-HCFO-1224yd 20 1 - 99/99 - 1
E-HFO-1336mzz/E-HCFO-1224yd 40 1 - 99/99 - 1
E-HFO-1336mzz/E-HCFO-1224yd 60 1 - 99/99 - 1
E-HFO-1336mzz/E-HCFO-1224yd 80 1 - 99/99 - 1
E-HFO-1336mzz/E-HCFO-1224yd 100 1 - 99/99 - 1
E-HFO-1336mzz/E-HCFO-1224yd 120 1 - 99/99 - 1
Table 2 Azeotrope-like compositions
Mole Percentage Range
COMPONENTS T (°C)
E-HFO-1336mzz/E-HCFO-1224yd - 40 5 - 95/95 - 5
E-HFO-1336mzz/E-HCFO-1224yd - 20 5 - 95/95 - 5
E-HFO-1336mzz/E-HCFO-1224yd 0 5 - 95/95 - 5
E-HFO-1336mzz/E-HCFO-1224yd 20 5 - 95/95 - 5
E-HFO-1336mzz/E-HCFO-1224yd 40 5 - 95/95 - 5
E-HFO-1336mzz/E-HCFO-1224yd 60 5 - 95/95 - 5
E-HFO-1336mzz/E-HCFO-1224yd 80 5 - 95/95 - 5
E-HFO-1336mzz/E-HCFO-1224yd 100 5 - 95/95 - 5
E-HFO-1336mzz/E-HCFO-1224yd 120 5 - 95/95 - 5
It was also found through experiments that E-HCFO-1224yd and E- HFO-1438mzz form azeotrope-like compositions.
To determine the relative volatility of this binary pair, the PTx method described above was used. The pressure in a PTx cell of known volume was measured at constant temperature for various binary compositions. These measurements were then reduced to equilibrium vapor and liquid compositions in the cell using the NRTL equation.
The pressures measured versus the compositions in the PTx cell for E-HFO-1438mzz/E-HCFO-1224yd mixture are shown in FIG. 2, which graphically illustrates the formation of azeotrope-like compositions of E- HFO-1438mzz and E-HCFO-1224yd at 31 .8 °C, as indicated by mixtures of about 1 to 33 mole % E-HFO-1438mzz and about 99 to 67 mole % E- HCFO-1224yd at pressures ranging from about 25 psia to about 28 psia, and mixtures of about 84 to 99 mole % E-HFO-1438mzz and about 16 to 1 mole % E-HCFO-1224yd at pressures ranging from about 16 psia to about 19 psia. According to calculation, azeotrope-like compositions consisting essentially of 1 -99 mole % E-HFO-1438mzz and 99-1 mole % E-HCFO- 1224yd are formed at temperatures ranging from about -40 °C to about 140 °C (i.e., over this temperature range, the difference in dew point pressure and bubble point pressure of the composition at a particular temperature is less than or equal to 5 percent (based upon the bubble point pressure)).
Some embodiments of azeotrope-like compositions are listed in Table 3. Some more embodiments of azeotrope-like compositions are listed in Table 4.
Table 3 Azeotrope-like compositions
Table 4 Azeotrope-like compositions E-HFO-1438mzz/E-HCFO-1224yd - 40 5 - 1 1/95 - 89 and
96 - 99/4 - 1
E-HFO-1438mzz/E-HCFO-1224yd - 20 5 - 14/95 - 86 and
94 - 95/6 - 5
E-HFO-1438mzz/E-HCFO-1224yd 0 5 - 19/95 - 81 and
92 - 95/8 - 5
E-HFO-1438mzz/E-HCFO-1224yd 20 5 - 26/95 - 74 and
88 - 95/12 - 5
E-HFO-1438mzz/E-HCFO-1224yd 40 5 - 38/95 - 62 and
80 - 95/20 - 5
E-HFO-1438mzz/E-HCFO-1224yd 60 5 - 95/95 - 5
E-HFO-1438mzz/E-HCFO-1224yd 80 5 - 95/95 - 5
E-HFO-1438mzz/E-HCFO-1224yd 100 5 - 95/95 - 5
E-HFO-1438mzz/E-HCFO-1224yd 120 5 - 95/95 - 5
E-HFO-1438mzz/E-HCFO-1224yd 140 5 - 95/95 - 5
The azeotrope-like compositions of the present invention can be prepared by any convenient method including mixing or combining the desired amounts. In one embodiment of this invention, an azeotrope-like composition can be prepared by weighing the desired component amounts and thereafter combining them in an appropriate container.
The azeotrope-like compositions of the present invention can be used in a wide range of applications, including their use as aerosol propellants, refrigerants, solvents, cleaning agents, blowing agents (foam expansion agents) for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
One embodiment of this invention provides a process for preparing a thermoplastic or thermoset foam. The process comprises using an azeotrope-like composition as a blowing agent, wherein said azeotrope- like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E- HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
Another embodiment of this invention provides a process for producing refrigeration. The process comprises condensing an azeotrope- like composition and thereafter evaporating said azeotrope-like
composition in the vicinity of the body to be cooled, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
Another embodiment of this invention provides a process using an azeotrope-like composition as a solvent, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E- HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
Another embodiment of this invention provides a process for producing an aerosol product. The process comprises using an azeotrope- like composition as a propellant, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz;
wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
Another embodiment of this invention provides a process using an azeotrope-like composition as a heat transfer media, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
Another embodiment of this invention provides a process for extinguishing or suppressing a fire. The process comprises using an azeotrope-like composition as a fire extinguishing or suppression agent, wherein said azeotrope-like composition consists essentially of (a) E- HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E-HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.
Another embodiment of this invention provides a process using an azeotrope-like composition as dielectrics, wherein said azeotrope-like composition consists essentially of (a) E-HCFO-1224yd and (b) a component selected from the group consisting of E-HFO-1336mzz and E- HFO-1438mzz; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-HCFO-1224yd.

Claims

1 . A composition consisting essentially of:
(a) E-1 -chloro-2,3,3,3-tetrafluoropropene; and
(b) a component selected from the group consisting of E- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene and E-1 ,1 ,1 ,4,4,5,5,5-octafluoro-2- pentene; wherein said component is present in an effective amount to form an azeotrope-like combination with the E-1 -chloro-2, 3,3,3- tetrafluoropropene.
2. A process for preparing a thermoplastic or thermoset foam
comprising using the azeotrope-like composition of Claim 1 as a blowing agent.
3. A process for producing refrigeration comprising condensing the azeotrope-like composition of Claim 1 and thereafter evaporating said azeotrope-like composition in the vicinity of the body to be cooled.
4. A process comprising using the azeotrope-like composition of Claim 1 as a solvent.
5. A process for producing an aerosol product comprising using the azeotrope-like composition of Claim 1 as a propellant.
6. A process comprising using the azeotrope-like composition of Claim 1 as a heat transfer media.
7. A process for extinguishing or suppressing a fire comprising using the azeotrope-like composition of Claim 1 as a fire extinguishing or suppression agent.
8. A process comprising using the azeotrope-like composition of Claim 1 as dielectrics.
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Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HK1198174A1 (en) * 2011-10-20 2015-03-13 E. I. Du Pont De Nemours And Company Azeotrope-like compositions of e-1-chloro-2,3,3,3-tetrafluoropropene and uses thereof
US8927666B2 (en) * 2012-11-08 2015-01-06 Honeywell International Inc. Polymerization of monomers using fluorinated propylene solvents
WO2014080868A1 (en) * 2012-11-20 2014-05-30 旭硝子株式会社 Working medium for rankine cycle, and rankine cycle system
DE102014220985A1 (en) * 2014-07-03 2016-01-07 Siemens Aktiengesellschaft Apparatus and method for using 1,1,1,4,4,4-hexafluoro-2-butene as a gaseous, electrically insulating and / or arc-extinguishing medium
WO2016146197A1 (en) * 2015-03-19 2016-09-22 Abb Technology Ag Dielectric insulation or arc-extinction fluid
EP3287503A4 (en) * 2015-04-24 2018-12-19 AGC Inc. Composition for use in heat cycle system, and heat cycle system
US10400149B2 (en) 2015-04-27 2019-09-03 Trane International Inc. Improving glide in refrigerant blends and/or azeotopic blends, alternatives to R123 refrigerant, and refrigerant compositions, methods, and systems thereof
US9944839B2 (en) 2015-04-27 2018-04-17 Trane International Inc. Refrigerant compositions
EP3418651A4 (en) * 2016-02-19 2019-10-16 Agc Inc. CALORIFIC CYCLE SYSTEM AND CALORIFIC CYCLE METHOD USING THE SAME
WO2018021275A1 (en) * 2016-07-29 2018-02-01 旭硝子株式会社 Working medium for heat cycles
JP2018153463A (en) * 2017-03-17 2018-10-04 Ａｇｃ株式会社 Fire-extinguishing agent composition and fire-extinguishing system
JP2020520259A (en) * 2017-05-08 2020-07-09 ハネウェル・インターナショナル・インコーポレーテッドＨｏｎｅｙｗｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｉｎｃ． HFO-1224YD Fire Fighting Compositions, Systems and Methods
WO2019036049A1 (en) * 2017-08-18 2019-02-21 The Chemours Company, Fc, Llc Compositions and uses of z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene
EP4335780A3 (en) 2017-09-28 2024-05-22 AGC Inc. Sprayer
CN111263780B (en) * 2017-11-01 2022-04-05 Ａｇｃ株式会社 Method for producing hard foamed synthetic resin
WO2020054306A1 (en) * 2018-09-12 2020-03-19 Ａｇｃ株式会社 Fire extinguishing agent, fire extinguishing agent composition and fire extinguishing system using said fire extinguishing agent or fire extinguishing agent composition
JP7141983B2 (en) * 2019-07-01 2022-09-26 旭有機材株式会社 Resin composition for producing phenolic foam, phenolic foam and method for producing the same
CN114945470B (en) * 2020-01-16 2024-07-30 旭化成建材株式会社 Phenolic resin foam laminate and composite board
WO2021157698A1 (en) * 2020-02-06 2021-08-12 旭化成建材株式会社 Phenol resin foam laminate
WO2022085544A1 (en) * 2020-10-22 2022-04-28 Ａｇｃ株式会社 Electric equipment
US12054596B2 (en) * 2020-11-30 2024-08-06 Honeywell International Inc. Azeotrope or azeotrope-like compositions of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z))
WO2022191203A1 (en) * 2021-03-11 2022-09-15 Ａｇｃ株式会社 Aerosol raw material composition, aerosol composition, and aerosol product
JP7759962B2 (en) * 2021-03-30 2025-10-24 ハネウェル・インターナショナル・インコーポレーテッド Blowing agent containing Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z))

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4305163A1 (en) 1993-02-19 1994-08-25 Bayer Ag Process for the preparation of hexafluorobutene
US20110152392A1 (en) * 2009-12-17 2011-06-23 Honeywell International Inc. Catalysts For Polyurethane Foam Polyol Premixes Containing Halogenated Olefin Blowing Agents
BRPI0619713B1 (en) 2005-11-01 2018-02-06 E. I. Du Pont De Nemours And Company Heating or cooling production method and original heat transfer fluid or refrigerant composition replacement method
US7335804B2 (en) * 2005-11-03 2008-02-26 Honeywell International Inc. Direct conversion of HCFC 225ca/cb mixture
MY160614A (en) * 2006-02-28 2017-03-15 Du Pont Azeotropic compositions comprising fluorinated compounds for cleaning applications
EP2091899A2 (en) * 2006-10-31 2009-08-26 E.I. Du Pont De Nemours And Company Processes for producing 2,3,3,3-tetrafluoropropene, a process for producing 1-chloro-2,2,3,3,3-pentafluoropropane and azeotropic compositions of 1-chloro-2,3,3,3-tetrafluoropropene with hf
RU2006139128A (en) 2006-11-07 2008-05-20 Е.И.Дюпон де Немур энд Компани (US) METHOD FOR PRODUCING FLORATED OLEFINS
WO2008079265A1 (en) * 2006-12-20 2008-07-03 E. I. Du Pont De Nemours And Company Process for the synthesis and separation of hydrofluoroolefins
CA2681872C (en) 2007-03-29 2015-06-09 Arkema Inc. Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US8618339B2 (en) 2007-04-26 2013-12-31 E I Du Pont De Nemours And Company High selectivity process to make dihydrofluoroalkenes
EP2152833B1 (en) * 2007-06-12 2014-07-23 E. I. Du Pont de Nemours and Company Azeotropic and azeotrope-like compositions of e-1,1,1,4,4,4-hexafluoro-2-butene
AU2008296223B2 (en) * 2007-09-06 2013-07-04 E. I. Du Pont De Nemours And Company Azeotropic and azeotrope-like compositions of E-1,1,1,4,4,5,5,5-Octafluoro-2-pentene
CN102307832A (en) * 2009-02-11 2012-01-04 阿克马法国公司 Azeotrope and azeotrope-like compositions of chlorotrifluoropropene and pentane
TW201107273A (en) 2009-06-02 2011-03-01 Du Pont Azeotropic and azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene
FR2948679B1 (en) * 2009-07-28 2011-08-19 Arkema France HEAT TRANSFER METHOD
WO2012106565A2 (en) 2011-02-04 2012-08-09 E. I. Du Pont De Nemours And Company Azeotropic and azeotrope-like compositions involving certain haloolefins and uses thereof
US9556303B2 (en) * 2011-02-21 2017-01-31 Honeywell International Inc. Catalysts for polyurethane foam polyol premixes containing halogenated olefin blowing agents
HK1198174A1 (en) * 2011-10-20 2015-03-13 E. I. Du Pont De Nemours And Company Azeotrope-like compositions of e-1-chloro-2,3,3,3-tetrafluoropropene and uses thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013059550A2 *

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CN103890065B (en) 2016-02-03
WO2013059550A3 (en) 2013-11-21
US20140305667A1 (en) 2014-10-16
AU2012325962B2 (en) 2016-05-19
JP6069335B2 (en) 2017-02-01
US8961808B2 (en) 2015-02-24
JP2014530939A (en) 2014-11-20
CA2852935C (en) 2017-06-20
EP2768893B1 (en) 2016-04-06
HK1198174A1 (en) 2015-03-13
CN103890065A (en) 2014-06-25
AU2012325962A1 (en) 2014-04-24
WO2013059550A2 (en) 2013-04-25
CA2852935A1 (en) 2013-04-25

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